Azodyestuffs insoluble in water and fibers dyed therewith



Patented Sept. 17, 1935 UNITED STATES- PATE. NT. OFFICE AZODYESTUFFS INSOLUBLE 11v WATER, AND v FIBERS DYED THEREWITH Werner Zerweck and Karl Schiitz, Frankfort-onthe-Main-Fechenheim, Germany, assignors to 7 77 General Aniline Works, Inc., New York, N. Y.,

a corporation of Delaware No Drawing. Application May 15, 1934, Serial 7 No. 725,820. In Germany May 23, 1933 8 Claims. (01. 260-95) 7 The present invention relates to new azodyestuffs insoluble in water more particularly to such corresponding to the general formula (wherein R1 means an aryl or aralkyl radical and R2 a combining component of-the group consisting of arylamides of acyl-acetic acids and orthohydroxy-aryl-carboxylic acids).

The dyestuffs may be prepared by combining in substance or on the fiber or on a substratum a 5 diazocompound of an amine 30.; Lasample 1 50 grams of cotton yarn are treated for half an hour with 1 liter of the following impregnating bath (a) squeezed or centrifugated; thewet ma-.

terial is then dyed in the developing bath (1)). Thereupon it is rinsed, soaped at thejboil and dried.

(a) Impregnating bath: V 7 grams of (2'-hydroxy-3'-naphthoylamino.),-

10 cc. of Turkey red oil of 50% strength and 10.5 cc. of caustic soda solution of 34 B, T0 the solution 2.7 cc. of formaldehyde of 30% strength are added and the Whole'is then made up'with cold water-to- 1liter."'

(b) Developing bath:

sulfone are diazotized with cc. of hydrochloric acid normal and 5 cc. of a normal sodium nitrate solution. After the addition of cc. of glacial acetic acid the hydrochloric acid 5 is neutralized by means of a solution of sodium acetate. Then i r V 30 grams of sodium chloride are added and the whole is made up with Water to 1 liter.

A vivid golden-orange dyeing of remarkable fastness qualities is obtained.

' Ewmr 2 Into an aqueous suspension of 26.3'grams of 2'- hydroxy-3'-naphthoyl-amino-benzene, prepared by. dissolving ,the, said arylide in an alcoholic caustic soda solution, diluting with Water and neutralizing with acetic acid, a diazo solution, prepared in the usual manner from 26.1 grams of 4-tolyl-2-amino benzyl-sulfone, is allowed to run in. The bright scarlet-red dyestuif separates in the form of flakes. When coupling is finished it is filtered with suction andwashed until neutral.

In the same manner similar clear yellowish orange shades may be obtained according to one of the usual printing methods.

The following table shows the shades of some 4 1 benzene are dissolved at boiling, temperafurther dyestuffs obtained according to the pres- 40 ture with 1 cut process: i p

Diem-component: Coupling component: Shade:

'4-c111orophenyl-2-amino-benzyl-sulione 1-(2-hydroxy-3-naphthoyl-amino)-2-methoxy-benzene Scarlet.

Dn l-(2-hydroxy-3-naphthoyl-amino)-4-chloro-benzene Full yellowish orange. Do 1g-hydroxy-3-naphthoyl-amino)-2-methyl-4- c h l o r o Bright scarlet.

enzene. Do 1-(2-hydroxy-3-naphthoyl-amino)-3-nitrobenzene Bluish red. Do 2-(2-hydroxy-3-naphthoyl-amino) -naphtha1ene Orange. 50 Do 4, 4-di-(acetoacetylamino)-3, 3-dimethyl-diphenyl Vilvid greenish yelow. 4'-chlorophenyl-ai-amino-benzylsulfcn Red.

Do Yellowish red. Do Red. 4-n1]e)thylphenyl-2-amino-benzylsulfone Vivig scarlet. n o. Do Brown. 55

Diem-component: Coupling component: Shade:

4'-ch10ro-phenyl-4-methoxy-3-amino-benzyl-sulfone (2'-hydroxy-3-naphthoy1-amino)-benzene Very bright red.

D 1-(2-hydroxy-3-naphthoyl-an1ino)-2-methoxy-benzene- Do. 5 Dn 2-(2-hydroxy-3-naphthoyl-amino)-naphthalene Do. go. i-gi-lfiiygroxy-gi-napgfilfioyl'aminoggiapitliaalend- Vivig bluish red.

0 Y I'OXY- -nap oy -am1no 'Dl 1'0 enzene- O. 4-methylphenyl-4-a.mino-benzyl-sulfone (2-hydroxy-3'naphthoyl-arnino)-benzene Red. Phe%yl-2-amino-benZyl-sulfone l-gfgygroxy-g;-napg%%oy}-aminoglzenfiene gjqlid Sczglet. 1

0 y roxy- -nap 0y -ami11o -c oroe owis scar et. 3-ch]l)orophenyl-2-amino-benzyl-sultone" -(2 ilydrgxy-EV-napnghoyl-afnino)+llsnethyl-beiilzene Y11Do. 10

0 -ace oace yaminoenzoy-aminoenzt iazo e 0w. 2-chlorophenyl-Z-amino-benzyl-sulione 1-(2-hydr0xy-3-napl1thoyl-amino)-?rmethoxy-benzene Bluish red.

Dn 1-g-hydroxy-Zi-naphtl1oyl-amino)-2.S-dimethoxyAchloro- Do.

enzene. 3.4dieh1oro-phenyl-2-amino-benzyl-sulfone 1-(2-hYdroxy-3-naphthoyl-amino)-4-eth0xy-benzene Orange.

Do 7 2-acetoacetylamino-6-benzoyl-amino-benzthiazol Briglllrt greenish e ow. 4-ch]g)ro-phenyl-2-aminc-6-chloro-be11lyl-S11lf0De l-(2i-l ygroxygi-napf lzgoyl-aminogtenzetnefg golden-orange. 15

n y roxy- -nap oy -3.I1ll1l0 me yenzene range. 4-bromo-phenyl2-amino-benzyl-sulfone 1-(2-hydroxy-3'-naphthoyl-emino)-benzene Yellowishorange.

Do di-(aeetoaoetyD-o-tolidine Vivid greenish yellow. 4-ch1oro-2.5-dimethyl-2-amino-benzyl-sulione l- (2-hydroxy-3-naphthoyl-amino)-3-oh1oro-6-methyl-ben- Scarlet.

Z8118. Dn terephtaloyl-di-(acetyl-amino-Z.4-dimethoxy-5-chloro-ben- Yellow. 20

Z9118 4 2-methoxyphenyl-2-amino-benzyl-sul[one 1-(2-hydroxy-3QnaphthoyI-amind)3-nitro-benzene Vivid scarlet.

2-acetoacetylamino-6-ethoxy-benzthiazol Greenish yellow. -gi-hlygroxygz-napgithoyl-agnnlo)benzengil?.ng grililnge. h b D0 y roxy- -car azo-car oy-amino c oroenzene. e owis rown. 4-benzene-sulfo-phenyl-2-amino-benzyl-sulfone -g-l ygrow-g1-11apggn oyl-arninog-benfinle1 otallljge. Do y roxy- -nap oy-amino -nap acne"... o. 3-benzene-sulf0-phenyl-2-amino-benzyl-sulione 1-(2-hydroxy-3-naphthoy1-amino)-2-methoxy-benzene. Bright scarlet. 25

D0 1-(2-l1ydroxy-3-naphthoy1amino)-2-methyl-4-chloro-ben- Do.

zene. phenyl-4-an1ino-benzyl-sulfone 1-(2'-hydroxy-3-naphthoyl-amino)-2-metl1oxy-benzene Red.

Dn 1-(2'-hydroxy-3-carbazol-carboyl-amino)-4-ch1oro-benzene Brown.

Since an object of the present invention is to 3. Azodyestuff of the formula: 30 provide dyestuffs of good fastness properties, 01 which dyestuffs are insoluble in water and alkalies, it is to be understood that the benzene nuclei of CFOSOFOH the general formulae appearing in the appended claims do not contain any substituents which are t 35 known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid, the carboxylic acid and the hydroxy group.

We claim:

1. Azodyestufis corresponding to the general formula:

wherein R1 means a radicleof the benzene series and R2 a combining component of the group consisting of arylamides of acylacetic'acids and ortho-hydroxy-aryl-carboxylic acids.

2. Azodyestufi of the formula:

which dyestuff yields when prepared on the fiber golden orange shades of a good fastness.

which dyestufi yields when prepared on the fiber golden orange shades of a good fastness.

4. Azodyestuff of the formula:

HZOOSOPGHPO 45 which dyestuff yields when prepared on the fiber 55 bright scarlet shades of a good fastness.

5. Fibers dyed with the dyestuffs claimed in claim 1.

6. Fibers dyed with the dyestufi claimed in claim 2. a

7. Fibers dyed with the dyestuif claimed in 60 claim 3.

8. Fibers dyed with the dyestuif claimed in KARL scrrii'rz. 

